Condensation product of phenol phthalein



'Patented Nov. 16, 1937.

'coNnE sA'noN PRODUCT or runner.

PHTHALEIN Edmond Ii. Buoy and Robert Watkins, Waukegan,

111., assignors to Atlas Powder Company, Wilmington, Del, a corporation of Delaware No Drawing. Application April 2, 1936,

' Serial No. 72,289

1c Claims. (01. 260-2) This invention relates to condensation prodnets ofphenol-phthalein with rosin, with or without non-essential vegetable oils such as castor oil, linseed 011, China wood oil, etc. and is 5 a continuation-in-part of our co-pending application, Serial Number 629,878, filed August 22, 1932, now Patent No. 2,085,183. (I a It is well known that the synthetic resins made by the reaction between a phenol and an aldehyde, or substances developing aldehydes, have found great use in the manufacture of varnish and lacquers. even though their undesirable property of turning red or pink requires great attention and care in their manufacture. However, even with the greatest care such changes in the color cannot always be avoided and cause waste in material, time and labor.

In addition to this hardship, there is the other that cellulose ester solutions, such as that of nitro-cellulose, cellulose acetate, and those of the cellulose ethers are not compatible with the various classes of resins, or solutions of the same.

Thus, synthetic resins may not always be dissolved in solvents of either intro-cellulose or cellulose acetate, or solutions of such synthetic resins are not miscible with solutions of the aforesaid cellulose derivatives. Another question to be considered is whether the synthetic resin, if it blends well with the solution of aforesaid cellulose compounds upon evaporation of the solvent, furnishes a film which, if durable, flexible and elastic enough to be acceptable, has the proper luster and gloss.

Although the present market offers various synthetic resins of substantial merit, there is a need for synthetic resins having all the desirable merits of the best known synthetic resins and yet free of the bothersome discolorations heretofore mentioned.

We have found that we may obtain very desirablesynthetic resins for the purpose of admixing the same to nitro-acetyl cellulose, or cellulose ethers, by condensing phenol-phthalein with rosin, with or without the addition of various non-essential vegetable oils, such as linseed oil, boiled linseed oil, China wood oil, rape-seed oil, castor oil, olive oil, peanut oil, and other similar oils which are more or less often applied in the line of this art, and various acids such as pa]- mitic, stearic, -linolelc, linolenic, oleic, etc., and mixtures thereof. A

Our new compounds may be easily introduced t anitro-cellulose solution, or acetyl-cellulose solution, or into solutions of cellulose ethers,

such'as methyl-cellulose, ethyl-cellulose, propylcellulcse, butyl-cellulose and amyl-cellulose.

Benzyl-cellulose and acetyl-cellulose, or their solutions, arev representative of the complete series of ethe'rs with which our new synthetic 5 resins, or their solutions, readily blend so as to yield clear and tough films for moving picture purposes, or for coating surfaces of metals, wood, or of cementitious or other compositions, such as used in the building trade. Our new comw poundsmay be suitably used as binders in the molding of all kinds of articles from mixtures of plastic products. In the application ofour new resins and the compositions made therefrom, it is of course understood that both natural 15 gums and synthetic resins may be admixed there with, for instance, phenol-formaldehyde con-= densation products, novolaks, urea-formaldehyde condensation products, resins consisting of glycerin esters and other similar products.

In order that our invention may be clearly understood, we wish to describe the procedure of making the various synthetic resins, all of which contain the radical of phenol-phthaleln in their molecule.

I.--Process for condensing phenol-phthalein with rosin We mix 1 lb. of rosin with 8 oz. of phenolphthalein and heat the mixture, suitably under a 3 reflux condenser, in an oil bath up to 480 F.; after this temperature is reached we let the mixture cool down to 420 F. and keep it at this temperature until the reaction is complete, which is noted by the uniformity and clarity of the re- 35 action products. We had cause to notice that the aforesaid temperatures are critical for the result of the process and that the heating should be carefully confined to said temperatures as otherwise the final product will assume a crystalso lineform instead of remaining in the amorphous state, which is preferable for various purposes. The crystalline product was found to melt at C. (113 F).

The above description applies when the react- 45 mg materials are used without modifiers or catalysts. It is possible by using such modifiers to obviate the necessity of working at such a critical temperature, although with modifiers the first temperature to which the mixture is heated is preferably at least 460 F. and the second temperature to which the reacting mixture is cooled is'preferably not greater than 440 F. Therefore, with modifiers or a catalyst, a first temperature ange of from 460 to 480 F. and a second temscribed and claimed in our co-pending applicaligature range of from 420 to 440 F. are suit- ,a e.

" The resin thus obtained is soluble in esters, for instance, in the acetates, such as ethyl, amyl, butyl and propyl acetates, the propionates, such as butyl-propionate, the lactates, such as ethyllactate, cellosolve acetate, and the complete series of esters, also alcohols, such as methyl alcohoi, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, ketones, such as acetcnes, acetates, ethyl-ketone, ethyl-acetone, methyl-acetone, ethyl-methyl-ketone, camphor oil, acetone oil, and other similar solvents.

These resins are for the most part sparingly soluble in coal-tar and petroleum hydrocarbons, but are readily soluble in mixtures of such hydrocarbons when mixed with alcohol or other solvents mentioned above.

The reaction between the phenol-phthalein and the rosin proceeds without or with pressure, with a speed quite satisfactory for technical purposes. We found, however, that the speed of reaction may be remarkably accelerated by adding various accelerating agents to the mixture of the reacting substances; they may be added in an amount of approximately 10% of the phenol-phthalein content (this percentage, however, is not critical and may be varied quite widely one way or the other) to the mixture either before or after the heating has been started. We found it'convenient to evenly distribute the accelerating agent through the mixture before the same is heated as this guarantees a more even effect on the molten batch. As accelerating or modifying agents we found particularly suitable p-tertiary amyl-phenol, sodium carbonate; other fairly good agents for this purpose are hydrochloric acid and sodium benzoate.

Although the process of condensing phenolphthalein with non-essential vegetable oils is detion above referred to, we have found that remarkable results may be obtained by condensing phenol-phthalein, rosin, and a non-essential vegetable oil. Examples of such resins are as follows:

IL-Phenol-phthalein, rosin, and castor oilmelting point 87 C.

IlI.Phenol-phthalein, rosin, wood oil-melting point 90 C.

-IV.-Phenol-phtha1ein, rosin, and linseed oilmelting point 85 C.

We may also, in the cases 11 to IV, apply with success accelerating agents such as p-tertiary amyl -phenol, sodium carbonate, sodium benzoate, and hydrochloric acid.

The mixtures mentioned above were treated as described-above under Example I and the and China amorphous condensation products obtained thereby are soluble in practically all the organic solvents usually applied in the manufacture of varnishes and lacquers except that the products obtained under Examples 11 to IV are insoluble in straight coal-tar and hydrocarbons.

The condensation products of phenolphthalein with the various substances referred to in Examples I to. IV are all compatible with nitrocellulose, acetyl-cellulose, orcellulose ethers, for' the resins thus obtained dissolve entirelyin solu-,= vtions of the aforesaid cellulose derivatives and the films obtained with them are absolutely'elear and transparent. Their mechanical strength is also highly satisfactory, the. film being strong and tough andhighly resistant to.

The adaptability of our new, condensation products is shown by the following examples illustrating the application of the new condensation products in lacquer compositions containing nitro-cellulose, acetyl-cellulose, and cellulose ethylether:

20"-30 nitro-cellulose cu 5 B.C'ellulose acetate lacquer Pounds 3 lb. cut of resin in ethyl lactate 4 Acetone Ethylene dichloride V2 /2 Completely denatured alcohol..- ti A lb. cellulose acetate solution 5 C.-Lacquer containing cellulose e'thulether I Pounds 4 lb. cut of resin 3 Completely denatured alcohol /2 Toluol $6 /2 lb. ethylether cellulose cut 5 Plasticizing agents may be added to the aforesaid lacquers aswell as to films such as may be obtained from any solution of such a condensation product with a nitro or acetyl-cellulose solution, or with a cellulose ether, such as cellulose ethylether.

Upon drying any of the aforesaid lacquers on a glass plate under special conditions, the films obtained may be easily stripped off and are absolutely clear and transparent so that their suitability for photographic purposes is well established. As to their mechanical solidity, it may be-said that they are very hard and tough and that they cannot be scratched by passing a finger nail over them.- I Y Our new synthetic resins are suitable for makiiig molded articles from the synthetic resins obtained as described above, eitherby these resins as suchor in admixture with any of the'many fillers as applied in the molding, for instance, asbestos, wood flour, silica-earth, since the resins have a melting point below 100 C. and thus can be conveniently melted by simply heating the mold with steam in a the art. I

whatweclaimisasfollows:

1. A synthetic resin of the condensation product of phenol-phthalein, resin, and a non-essential vegetable oil," said product having a melting point in the neighborhood of to C.

2'. A synthetic resin consisting of the condensation product of .phenol-phthaleim rosin and a non-essential vegetable oil taken from the group consisting of castor oil, linseed oil and China woodioil. said product having a melting point in the neighborhood of 85 to 90 C.

3. A synthetic ruin consisting of a condensation product of phenol-phthalein. rofln and castor oil, said product having a melting point' in the neighborhood of er c.

4. A syntheticresin consisting of the condensation product of phencl-phthalein,

manner well-known to roslnandwhich comprises heating a mixture of phenol-v densation product phthalein and rosin to a temperature in the neighborhood of 480 F.,- cooling the mixture to a temperature ,in the neighborhood of 420 1".,

Y and maintaining the temperature in the neighborhood of 420 1'. until the reaction mass has become entirely clear. 7 Y "I. The process or making an amorphous con- 01 phenol-phthalein, rosin, and

a non-essential tegetable oil which comprises heating a mixture of phenol-phthalein, rosin and said oil to a temperature oi-i'rom 460 to 480' F., cooling the mixtureto a second temperature of from 420 to 440 E, maintaining the temperature until the reaction 'mass has become entirely clear, and the oiiy part oi! the reaction product from the reaction mass.

8, The process of making a resinous material comprising the condensation product 01 phenolphthalein and rosin'which comprises heating together the phenol-phthalein a'n'd rosin in the presence of an agent selected mm the group consisting of sodium carbonate, sodium benzoate, 1

p-tertiary amyi-phenol and hydrochloric acid.-

9. The process of making a resinous material comprising the condensation product of phenolphthalein. rosin and a non-essential vegetable oil which comprises heating together phenolphthalein, rosin and said oil in the presence of an agent selected from the group consisting oi. sodium carbonate, sodium benzoate, p-tertiary amyl-phenol and hydrochloric acid.

10. The'process of making a resinous material comprising the condensation product of phenolphthalein and rosin which comprises heating together pheno'l-phthalein and rosin in the presence or p-tertiary amyl-phenoi.

11. The processor making a resinous material comprising the condensation product of phenolphthalein, rosin, and a non-essential vegetable oil which comprises heating the phendl-phthalein, rosin andnon-essential gegetable oil in the presence of p-tertiary amyi-phenoi.

12. A synthetic resin comprising an amorphous condensation product of phenoi-phthalein and made in accordance with the processor EDMOND H. BUCY. ROBERT WATKINS. 

